JP2009157233A - Antireflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film on which interference fringes are inconspicuous and that has good balance between transparency and anti-static properties and does not generate smog (blur) during manufacturing. <P>SOLUTION: The antireflection film has a hard coat layer on biaxially oriented PET and further has a low refractive index layer on the hard coat layer. The hard coat layer has a thickness of 0.5-5 μm and is formed by blending a 200-600 pts.mass mixture of gallium dope zinc oxide and antimonic acid zinc (here, the former : the latter is 9:1 to 1:9 (mass ratio)) into 100 pts.mass ionizing radiation curable resin and curing the blended product. The low refractive index layer is formed of composition for low refractive index layer formation containing matrix component mainly containing organic disilane compound containing fluorine atoms and hollow silica particles processed with a silane coupling agent. The composition is formed by blending 20-160 pts.mass hollow silica particles into 100 pts.mass matrix component. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antireflection film, and in particular, relates to an antireflection film in which interference fringes are not conspicuous, the minimum reflectance is low, and transparency, steel wool resistance, antistatic properties, and curl properties are excellent. It is.

  A display such as a personal computer, a television, a car navigator, or a mobile phone is one in which a person views an image and reads information, and visibility is required as an important function. However, in reality, there are many situations in which the contrast due to the reflection of the background decreases and the screen becomes difficult to see. In order to prevent this, a device for suppressing the surface reflection of the screen, which causes a reduction in visibility, is made, and the display surface is subjected to an antiglare treatment or an antireflection treatment.

The anti-glare process is a process of forming fine irregularities on the surface of the display and scatter the reflected image by scattering light to blur the outline. When the substrate is plastic, inorganic fine particles such as silica and organic fine particles such as polystyrene are coated on the surface, but the resolution of the image is lowered. In the antireflection treatment, a thin film having a thickness of about the wavelength of light is formed on the surface, and the reflectance is reduced by the light interference effect. When the refractive index of the incident medium is n ₁ , the refractive index of the film is n ₂ , and the reflectance is R,
R = [(n ₂ −n ₁ ) / (n ₂ + n ₁ )] ²
Where d is the film thickness and λ is the wavelength of the light.
d = λ / (4n ₂ )
In this case, the light interference effect is maximized.

As a method for forming a thin film, there are a dry method and a wet method. In the dry method, a high refractive index layer such as titanium dioxide and a low refractive index layer such as magnesium fluoride or silica are formed by vacuum deposition or sputtering. It takes time and is difficult to continue.
As for the wet method, for example, in the antireflection film obtained by laminating a high refractive index hard coat layer and a low refractive index layer directly or via another layer on a transparent substrate film, the low refractive index layer is R _n Si (OR ′) _n (R and R ′ represent an alkyl group having 1 to 10 carbon atoms, m + n is 4, and m and n are each an integer) to hydrolyze a silicon alkoxide represented by An antireflection film comprising an SiO ₂ gel layer formed from an adjusted SiO ₂ sol solution is disclosed (Patent Document 1). However, since the antireflection film has a high minimum reflectance, a sufficient antireflection effect cannot be obtained, the alkali resistance and the ultraviolet ray cutting property are inferior, and the interference fringes are not sufficiently satisfied.

Further, it is characterized in that it contains silicon alkoxide, a nonaqueous solvent, and porous silica fine powder having an average particle diameter of 0.3 to 100 nm and a refractive index of 1.2 to 1.4. A coating material for forming a low refractive index film is disclosed (Patent Document 2). However, the antireflective film having a low refractive index formed by using the coating material for forming a low refractive index film has improved antireflective effect, but is inferior in transparency, alkali resistance, and ultraviolet cut property. The above prescription has a problem that smog (whitening) occurs during production.
JP-A-10-726 Japanese Patent No. 3272111

  Therefore, the object of the present invention is that interference fringes are not conspicuous, the minimum reflectance is low, the properties are excellent in transparency, steel wool resistance, antistatic properties and curling properties, and the balance between transparency and antistatic properties is achieved. An object of the present invention is to provide an antireflection film that is excellent in improving alkali resistance and free from smog (whitening) during production.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have a hard coat layer having a specific thickness and material structure on a base film made of biaxially stretched polyethylene terephthalate, and a specific material. It has been found that the above problem can be solved by sequentially providing a low refractive index layer having a configuration, and the present invention has been completed based on this finding.

That is, the present invention is as follows.
1. An antireflection film having a hard coat layer on a base film made of biaxially stretched polyethylene terephthalate, and further having a low refractive index layer on the hard coat layer,
The hard coat layer has a thickness of 0.5 to 5 μm,
The hard coat layer is a mixture of gallium-doped zinc oxide and zinc antimonate on 100 parts by mass of ionizing radiation curable resin containing polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule ( However, it is formed by blending 200 to 600 parts by mass of gallium-doped zinc oxide: zinc antimonate = 9: 1 to 1: 9 (mass ratio) and curing this,
The low refractive index layer is a hollow treated with a disilane compound having a divalent organic group containing one or more fluorine atoms or a matrix component mainly composed of a (partial) hydrolyzate thereof, and a silane coupling agent. Formed from a composition for forming a low refractive index layer containing silica particles,
The antireflective film, wherein the composition for forming a low refractive index layer is formed by blending 20 to 160 parts by mass of hollow silica particles treated with the silane coupling agent with respect to 100 parts by mass of the matrix component. .
2. 2. The antireflection film as described in 1 above, wherein 5 to 20 parts by mass of a polymer having an unsaturated double bond copolymerizable at a terminal is further blended with 100 parts by mass of the ionizing radiation curable resin.
3. 2. The antireflection film as described in 1 above, further comprising 0.5 to 20 parts by mass of an ultraviolet absorber in 100 parts by mass of the ionizing radiation curable resin.
4). 4. The antireflection film as described in 3 above, wherein the ultraviolet absorber is benzotriazole-based.
5. 2. The antireflection film as described in 1 above, wherein the polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule is dipentaerythritol hexaacrylate.
6). 2. The antireflection film as described in 1 above, wherein a primary particle diameter of the gallium-doped zinc oxide is 5 to 100 nm.
7). The disilane compound is represented by the following formula (1):
^{_{X m R 1 3-m Si}} -Y-SiR 1 3-m X m (1)
Wherein R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a divalent organic group containing one or more fluorine atoms, X is a hydrolyzable group, m is 1, 2 or 3. is there.)
2. The antireflection film as described in 1 above, wherein
8). 2. The antireflection film as described in 1 above, wherein the hollow silica particles treated with the silane coupling agent have an average particle diameter of 5 to 100 nm.
9. 2. The antireflection film as described in 1 above, wherein the silane coupling agent is a vinyl silane coupling agent.

  According to the present invention, a hard coat layer having a specific thickness and material configuration and a low refractive index layer having a specific material configuration are sequentially provided on a base film made of biaxially stretched polyethylene terephthalate. , Interference fringes are inconspicuous, minimum reflectance is low, transparency, steel wool resistance, antistatic properties, curling properties are excellent, and the balance between transparency and antistatic properties is excellent, improving alkali resistance Furthermore, it is possible to provide an antireflection film that does not generate smog (whitening) during production.

Hereinafter, the present invention will be described in more detail.
(Base film)
The base film used in the present invention is made of biaxially stretched polyethylene terephthalate having transparency. A biaxially stretched polyethylene terephthalate film is preferably used because of its good mechanical strength and dimensional stability.
The refractive index of the base film is usually 1.64 to 1.66. In addition, the refractive index as used in the field of this invention is the value measured using the Abbe refractometer according to JISK7142. Moreover, the thickness of a base film is 20-250 micrometers, for example.

(Hard coat layer)
The hard coat layer in the present invention must satisfy the following requirements (1) and (2).
(1) The thickness is 0.5-5 μm.
If thickness is less than 0.5 micrometer, pencil hardness will fall and steel wool resistance will also fall. When the thickness exceeds 5 μm, the interference fringe prevention effect is not exhibited. A preferred thickness is 0.8 to 4.0 μm, and a more preferred thickness is 1.2 to 3.0 μm.

  (2) A mixture of gallium-doped zinc oxide and zinc antimonate on 100 parts by mass of ionizing radiation curable resin containing polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule (however, gallium Polymer 5 having 200 to 600 parts by mass of doped zinc oxide: zinc antimonate = 9: 1 to 1: 9 (mass ratio) and optionally having a copolymerizable unsaturated double bond at the terminal It is formed by blending ˜20 parts by mass and curing it.

  As polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Examples include pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and epoxy acrylate. Preferable specific examples include pentaerythritol triacrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol pentaacrylate. Among them, dipentaerythritol hexa (meth) acrylate is particularly preferable. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

The mixture consists of gallium-doped zinc oxide and zinc antimonate. However, the compounding ratio of these inorganic compound particles is gallium-doped zinc oxide: zinc antimonate = 9: 1 to 1: 9 (mass ratio).
Gallium-doped zinc oxide is commercially available, and examples thereof include Hakusui Tech Co., Ltd., trade name Pasette GK-40, GK-1, Cai Kasei Co., Ltd., trade name Nanotech GZO dispersion, and the like. The doping rate of gallium is usually about several mass%, specifically 1 to 6 mass%.
Zinc antimonate is commercially available, and examples thereof include trade names Celnax CX-Z610M-F2, CX-Z-603M-F2, and CX-Z-201IP-F2 manufactured by Nissan Chemical Co., Ltd.
The average primary particle diameter of gallium-doped zinc oxide is preferably 5 to 100 nm. If it is in this range, transparency can be improved.
The average primary particle diameter of zinc antimonate is, for example, 5 to 100 nm, preferably 5 to 50 nm. Within this range, transparency is high and preferable.
As described above, the ratio of gallium-doped zinc oxide to zinc antimonate is 9: 1 to 1: 9 (mass ratio), preferably 7: 3 to 3: 7 as the former: the latter, and more preferably. Is 6: 4 to 4: 6.
According to the present invention, the combined use of gallium-doped zinc oxide and zinc antimonate makes it possible to obtain sufficient conductivity without reducing transparency.

  Examples of the polymer having an unsaturated double bond copolymerizable at the terminal include terminal methacrylate polymethyl methacrylate, terminal styryl polymethacrylate, terminal methacrylate polystyrene, terminal methacrylate polyethylene glycol, terminal methacrylate acrylonitrile-styrene copolymer, terminal methacrylate styrene. -A methyl methacrylate copolymer etc. can be mentioned, The mass mean molecular weight has preferable 5000-10000. Examples of commercially available polymers having an unsaturated double bond copolymerizable at the terminal include macromonomers AA-6, AS-6S, AN-6S, AW-6S (manufactured by Toagosei Co., Ltd.), and the like. Can do.

In the present invention, the hard coat layer is composed of 100 parts by mass of ionizing radiation curable resin containing a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups, and 200 to 600 parts by mass of the mixture. It is formed using the composition which mix | blended 5-20 mass parts of polymers which have an unsaturated double bond copolymerizable. When the blending ratio of the mixture is less than 200 parts by mass, the effect of preventing interference fringes and the effect of reducing the minimum reflectance are not exhibited. In addition, no antistatic effect is exhibited. When the blending ratio of the mixture exceeds 600 parts by mass, the effect of preventing interference fringes is not exhibited. In addition, the steel wool resistance deteriorates. If the polymer having an unsaturated double bond copolymerizable at the terminal is less than 5 parts by mass, the curling property is somewhat inferior, and if it exceeds 20 parts by mass, the haze is increased and the transparency is lowered.
A more preferable blending ratio is that the mixture can be copolymerized at 250 to 500 parts by mass and the terminal with respect to 100 parts by mass of the ionizing radiation curable resin containing a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups. It is 5-15 mass parts of polymers having an unsaturated double bond.

  A hard-coat layer can be formed by apply | coating the said composition as a coating material on a base film, drying, and making it harden | cure by ionizing radiation irradiation. There is no particular limitation on the ionizing radiation, and examples thereof include an electron beam, radiation, and ultraviolet rays. Among ionizing radiations, ultraviolet rays are particularly suitable because they are simple in equipment and easy to handle. By irradiating with ionizing radiation and crosslinking, a coating film having a pencil hardness of H or higher as defined in JIS K 5400 can be formed.

  When the ionizing radiation is ultraviolet, a photopolymerization initiator is usually added. There is no restriction | limiting in particular as a photoinitiator, For example, Irgacure 184,907,651,1700,1800,819,369 (made by Ciba Specialty Chemicals), Darocur 1173 (made by Ciba Specialty Chemicals), Ezacure KIP150, TZT (made by Nippon Shibel Hegner), Lucyrin TPO (made by BASF), Kayacure BMS (made by Nippon Kayaku), etc. are mentioned.

  Of course, the composition can be used in combination with various additives as required. For example, an ultraviolet absorber can be used in combination. The ultraviolet absorber is exemplified below. Examples of the benzotriazole include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole. 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-dicumylphenyl) phenylbenzotriazole 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H -Benzotriazol-2-yl) -phenol] and the like. Examples of the benzophenone series include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and the like. . Examples of the acrylate system include ethyl-2-cyano-3,3′-diphenyl acrylate and 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate. Examples of salicylates include phenyl salicylate and 4-t-butylphenyl salicylate. Examples of the oxanilide type include 2-ethoxy-2'-ethyloxalic acid bisanilide, 2-ethoxyn-5-t-butyl-2'-ethyloxalic acid bisanilide, and the like. The addition amount of the ultraviolet absorber is 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. In the present invention, a benzotriazole-based ultraviolet absorber is particularly preferred from the viewpoint of ultraviolet absorption effect.

The obtained hard coat layer preferably has a refractive index that is the same as or very close to that of a base film made of biaxially stretched polyethylene terephthalate. Thus, by setting both refractive indexes, the interference fringe prevention effect is further improved. The extremely approximate here means that the absolute value of the refractive index difference between them is 0.02 or less.
Moreover, in the antireflection film of the present invention, the hard coat layer can also have a high refractive index layer and can have a simple structure in which a low refractive index layer is provided thereon.

(Easily adhesive layer)
In the antireflection film of the present invention, an easy-adhesive layer may be provided between the base film and the hard coat layer for the purpose of improving the adhesion between them and improving the interference fringe prevention effect.
The easy adhesive layer in the present invention preferably has a refractive index of 1.56 to 1.62. Within this range of the refractive index, the effect of preventing interference fringes is further enhanced. A more preferable refractive index is 1.58 to 1.61.
Examples of the material for the easy-adhesive layer include those that satisfy the above refractive index range, are transparent, and improve the adhesion between the base film and the hard coat layer, such as acrylic resins, polyester resins, urethane resins, and the like. And the like. Although the thickness of an easily bonding agent layer is not specifically limited, For example, it is 50 nm-100 nm. The easy adhesive layer can be provided on the base film by a known coating technique.

(Low refractive index layer)
The low refractive index layer in the present invention is treated with a disilane compound having a divalent organic group containing one or more fluorine atoms or a matrix component mainly composed of a (partial) hydrolyzate thereof, and a silane coupling agent. It is formed from a composition for forming a low refractive index layer containing hollow silica particles.
In the present invention, the (partial) hydrolyzate indicates that it may be a partial hydrolyzate or a complete hydrolyzate. The main component in the matrix component means that it is contained in an active ingredient excluding the solvent in a proportion of 50% by mass or more, particularly 70% by mass or more.

The matrix component is mainly composed of a disilane compound having a divalent organic group containing at least one fluorine atom or a (partial) hydrolyzate thereof.
The disilane compound has the following formula (1)
^{_{X m R 1 3-m Si}} -Y-SiR 1 3-m X m (1)
Wherein R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a divalent organic group containing one or more fluorine atoms, X is a hydrolyzable group, and m is 1, 2 or 3. .)
Or a (partial) hydrolyzate thereof (hereinafter also referred to as component (i)).

Here, Y represents a divalent organic group containing 1 or more, preferably 4 to 50, particularly preferably 8 to 24, fluorine atoms. Specific examples thereof include the following. However, the present invention is not limited to this.
_{-C 2 H 4 - (CF 2} ) n -C 2 H 4 -
_{-C 2 H 4 -CF (CF 3} ) - (CF 2) n -CF (CF 3) -C 2 H 4 -
_{-C 2 H 4 -CF (C 2} F 5) - (CF 2) n -CF (C 2 F 5) -C 2 H 4 -
_{-C 2 H 4 -CF (CF 3} ) CF 2 -O (CF 2) n O-CF 2 CF (CF 3) -C 2 H 4 -
(However, n is 2-20.)
_{-C 2 H 4 -C 6 F 10} -C 2 H 4 -
_{-C 2 H 4 -C 6 F 4} -C 2 H 4 -

In order to express various functions such as antifouling properties and water repellency in addition to antireflection properties, it is preferable to contain a large amount of fluorine atoms. In addition, since the perfluoroalkylene group is rigid, it is preferable to contain as many fluorine atoms as possible for the purpose of obtaining a film having high hardness and high scratch resistance. If it contains a large amount of fluorine atoms, the alkali resistance is improved. Therefore, Y represents the following structure: —CH ₂ CH ₂ (CF ₂ ) _n CH ₂ CH ₂ —
_{-C 2 H 4 -CF (CF 3} ) - (CF 2) n -CF (CF 3) -C 2 H 4 -
(However, n is 2-20.)
In particular, —CH ₂ CH ₂ (CF ₂ ) _n CH ₂ CH ₂ — (n = 2 to 20)
Is preferred.

  Although it is necessary to satisfy | fill the value of 2-20 as n, More preferably, it is good to satisfy | fill the range of 4-12, Most preferably, 4-10. If it is less than this, various functions such as antireflection, alkali resistance, stain resistance and water repellency may not be obtained sufficiently, and if it is too much, sufficient crosslinking resistance will be obtained because the crosslink density will decrease. There are cases where it is not possible.

R ¹ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group, a phenyl group, and the like can be exemplified. A methyl group is preferred for obtaining good scratch resistance.

  m is 1, 2 or 3, preferably 2 or 3, and in order to obtain a particularly hard film, m = 3 is preferable.

X represents a hydrolyzable group. Specific examples include halogen atoms such as Cl, organooxy groups represented by OR ² (R ² is a monovalent hydrocarbon group having 1 to 6 carbon atoms), particularly methoxy group, ethoxy group, propoxy group, isopropoxy group, Examples include alkoxy groups such as butoxy groups, alkenoxy groups such as isopropenoxy groups, acyloxy groups such as acetoxy groups, ketoxime groups such as methylethyl ketoxime groups, and alkoxyalkoxy groups such as methoxyethoxy groups. Among these, an alkoxy group is preferable, and a silane compound having a methoxy group or an ethoxy group is particularly preferable because it is easy to handle and the reaction during hydrolysis is easily controlled.

Specific examples of the disilane compound satisfying the above include the following.
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 8 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 10 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 16 -C 2 H 4 -Si (OCH 3) 3
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OC 2 H 5) 3
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OC 2 H 5) 3
_{(CH 3 O) 2 (CH} 3) Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (CH 3) (OCH 3) 2
_{(CH 3 O) 2 (CH} 3) Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (CH 3) (OCH 3) 2
_{(CH 3 O) (CH 3} ) 2 Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (CH 3) 2 (OCH 3)
_{(C 2 H 5 O) (} CH 3) 2 Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (CH 3) 2 (OC 2 H 5)
_{(CH 3 O) 3 Si-} C 2 H 4 -CF (CF 3) - (CF 2) 4 -CF (CF 3) -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 -CF (CF 3) - (CF 2) 8 -CF (CF 3) -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 -CF (CF 3) - (CF 2) 12 -CF (CF 3) -C 2 H 4 -Si (OCH 3) 3
Among these, preferably,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 8 -C 2 H 4 -Si (OCH 3) 3
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OC 2 H 5) 3
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OC 2 H 5) 3
These disilane compounds are preferably used.

The disilane compound of the above formula (1) can be used in combination with an organosilicon compound containing a fluorine atom-substituted organic group represented by the following formula (2) or its (partial) hydrolyzate (component (ii)). .
Rf-SiX ₃ (2)
(In the formula, Rf is a monovalent organic group containing one or more fluorine atoms, and X is a hydrolyzable group.)

Here, Rf represents a monovalent organic group containing one or more fluorine atoms, preferably 3 to 25, particularly preferably 3 to 17, and specific examples thereof include the following.
CF ₃ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₃ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₅ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₉ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₁₁ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₇ CONHC ₃ H ₆ −
CF ₃ (CF ₂ ) ₇ CONHC ₂ H ₄ NHC ₃ H ₆ −
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ OCOC ₂ H ₄ SC ₃ H ₆ −
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ OCONHC ₃ H ₆ −
CF ₃ (CF ₂ ) ₇ SO ₂ NHC ₃ H ₆ −
_{C 3 F 7 O (CF (} CF 3) CF 2 O) p CF (CF 3) CONHC 3 H 6 -
(However, p is p ≧ 1, especially 1 to 3.)
Among these,
CF ₃ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₃ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ −
Is preferable because it does not contain a polar part. X is as described above.

Specific examples of the organosilicon compound containing a fluorine atom-substituted organic group that satisfies the above are exemplified below.
CF ₃ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ C ₂ H ₄ —Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₃ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₃ C ₂ H ₄ —Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₅ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ —Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₉ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₁₁ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ CONHC ₃ H ₆ —Si (OCH ₃ ) _{3
CF 3 (CF 2) 7 CONHC} 2 H 4 NHC 3 H 6 -Si (OCH 3) 3
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ OCOC ₂ H ₄ SC ₃ H ₆ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ OCONHC ₃ H ₆ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ SO ₂ NHC ₃ H ₆ —Si (OCH ₃ ) _{3
C 3 F 7 O (CF (} CF 3) CF 2 O) p CF (CF 3) CONHC 3 H 6 -Si (OCH 3) 3
(However, p is p ≧ 1.)
Among these, the following are preferable.
CF ₃ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₃ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ —Si (OCH ₃ ) ₃

In the present invention, the component (i) can be used alone without being used in combination with the component (ii). However, when the component (i) and the component (ii) are mixed and used, the component (i) It is necessary that the content be 60% by mass or more and less than 100% by mass. When the content of the component (i) is less than 60% by mass, the crosslinking density is lowered, and good scratch resistance cannot be obtained, so that the function as a protective film becomes insufficient, which is not preferable. More preferably, the content of component (i) is 95% by mass or more. Moreover, it is preferable that the content rate of (i) component is 99.5 mass% or less from the point of the addition effect of (ii) component.
Moreover, in this invention, you may use what cohydrolyzed the mixture of the said (i) component and (ii) component.

  The composition for forming a low refractive index layer in the present invention is mainly composed of component (i), a mixture of component (i) and component (ii), or a co-hydrolyzate thereof, but has an effect on various properties required. In the range not given, the following organosilicon compounds or (partial) hydrolysates thereof can be used.

  Examples of the organosilicon compounds that can be used in combination with the components (i) and (ii) include silicates such as tetraethoxysilane, alkylsilanes such as methyltrimethoxysilane, hexyltrimethoxysilane, and decyltrimethoxysilane, phenyl Silane coupling agents such as phenylsilanes such as trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane And various compounds. In particular, tetraalkoxysilane is effective when used in combination with the purpose of improving scratch resistance because it has the effect of increasing the crosslink density, but it tends to make the coating hydrophilic, alkali resistance, and stain resistance. In addition, since it may reduce various functions such as water repellency, it is better to avoid using a large amount. It is preferable that the amount is not more than part by weight, particularly not more than 2 parts by weight, particularly not more than 1 part by weight.

The compounds of the above formulas (1) and (2), or the organosilicon compounds that can be used in combination with the above components (i) and (ii) may be used as they are, or (partially) in a hydrolyzed form, or You may use in the form hydrolyzed in the following solvent. From the viewpoint of increasing the curing rate after coating, it is preferable to use the (partly) hydrolyzed form. The amount of water used for the hydrolysis is preferably such that the molar ratio of (H ₂ O / Si—X) is 0.1 to 10.

  For the hydrolysis, a conventionally known method can be applied. As this hydrolysis catalyst or hydrolysis / condensation curing catalyst, acids such as hydrochloric acid, acetic acid, maleic acid, sodium hydroxide (NaOH), ammonia, triethylamine Amine compounds such as dibutylamine, hexylamine, octylamine and dibutylamine, salts of amine compounds, bases such as quaternary ammonium salts such as benzyltriethylammonium chloride and tetramethylammonium hydroxide, potassium fluoride, fluorine Organic compounds such as fluorides such as sodium fluoride, solid acidic catalysts or solid basic catalysts (eg ion exchange resin catalysts), iron-2-ethylhexoate, titanium naphthate, zinc stearate, dibutyltin diacetate Metal salts of carboxylic acids, tetrabutoxy titanium, Organic titanium esters such as la-i-propoxytitanium, dibutoxy- (bis-2,4-pentanedionate) titanium, di-i-propoxy (bis-2,4-pentanedionate) titanium, tetrabutoxyzirconium, tetra Organic zirconium esters such as i-propoxyzirconium, dibutoxy- (bis-2,4-pentanedionate) zirconium, di-i-propoxy (bis-2,4-pentanedionate) zirconium, aluminum triisopropoxide, etc. Alkoxy aluminum compounds, organometallic compounds such as aluminum chelate compounds such as aluminum acetylacetonate complex, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyl bird Aminoalkyl-substituted alkoxysilanes such as methoxysilane and N- (β-aminoethyl) -γ-aminopropyltriethoxysilane are exemplified, and these may be used alone or in combination.

  The addition amount of this catalyst is 0.01 to 10 parts by mass, preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the (partial) compound to be hydrolyzed. If this amount is less than 0.01 parts by mass, it may take too long to complete the reaction or the reaction may not proceed. Moreover, when it exceeds 10 mass parts, it is disadvantageous in cost, and the obtained composition or hardened | cured material may color, or a side reaction may increase.

  The hollow silica particles are particles having an outer shell layer mainly composed of silica and having a porous or hollow interior. The average particle diameter of the hollow silica particles is preferably 5 to 100 nm, and more preferably 10 to 80 nm. The average particle diameter was determined by a dynamic light scattering method.

  The hollow silica particles in the present invention are treated with a silane coupling agent. Examples of the silane coupling agent include a substance containing a silanol group or generating a silanol group by hydrolysis. Furthermore, a silane coupling agent having a polymerizable functional group other than a silanol group is preferable. The silanol groups of these substances can undergo dehydration condensation reaction with the hydroxyl groups on the surface of the hollow silica particles, and the silane coupling agent is bonded to the surface of the hollow silica particles and is easily dispersed in the organic component. Examples of polymerizable functional groups other than silanol groups include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, acrylamide group, hydroxyl group, glycidyl group and the like.

  Examples of the substance having a polymerizable functional group other than the silanol group include TSL-8311, TSL-8350, TSL-8337, TSL-8370, TSL-8375 (manufactured by GE Toshiba Silicone), A- 9530 (manufactured by Shin-Nakamura Chemical), KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

By treating the hollow silica particles with a silane coupling agent, it is possible to suppress smog (whitening, a phenomenon that appears white and cloudy due to coating unevenness) that occurs when the low refractive index layer is formed. The reason is not clear, but it is considered that the uneven distribution of the hollow silica particles during drying was suppressed.
Among them, in the present invention, a vinylsilane coupling agent is preferable from the viewpoint of smog improvement effect. The vinylsilane coupling agent can be represented by, for example, R ₃ Si—CH ₂ ═CH ₂ (wherein R represents a hydrolyzable group such as an alkoxy group).
The processing amount of the silane coupling agent is, for example, 0.5 to 4% by mass, preferably 1 to 2% by mass with respect to the hollow silica particles.

  As described above, the composition for forming a low refractive index layer in the present invention is formed by blending 20 to 160 parts by mass of hollow silica particles treated with the silane coupling agent with respect to 100 parts by mass of the matrix component. . A more preferable blending ratio is 30 to 120 parts by mass of hollow silica particles with respect to 100 parts by mass of the matrix component. When the hollow silica particle is less than 20 parts by mass, the minimum reflectance is increased, and when it exceeds 160 parts by mass, the chemical resistance is deteriorated.

  In the present invention, it is also preferable to add a graft copolymer having a repeating unit formed using a radical polymerizable monomer as a trunk and a silicone as a branch to the composition for forming a low refractive index layer. is there. The graft copolymer is preferably a comb-shaped acrylic graft copolymer in which a trunk portion composed of repeating units is an acrylic polymer. Examples of the graft copolymer include products obtained by condensing a silicone represented by the following formula (3) and an acrylsilane compound represented by the following formula (4).

(In the formula, R ⁶ and R ^{7 each} represent a monovalent aliphatic hydrocarbon group, phenyl group or monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms. Q is a positive number of 1 or more.)

(Wherein R ⁸ represents a hydrogen atom or a methyl group. R ⁹ represents a methyl group, an ethyl group or a phenyl group, and two R ^{9 s} may be the same or different from each other. Z represents a chlorine atom or a methoxy group. Or represents an ethoxy group.)

The silicone represented by the formula (3) used here can be obtained as a commercial product, and those suitable for the purpose can be used. R ⁶ and R ⁷ in the formula (3) are monovalent aliphatic hydrocarbon groups, phenyl groups or monovalent halogenated hydrocarbons having 1 to 10 carbon atoms, and monovalent fatty acids having 1 to 10 carbon atoms. Examples of the group hydrocarbon group include a methyl group, an ethyl group, and an acyl group. Examples of the monovalent halogenated hydrocarbon include a 3,3,3-trifluoropropyl group and a 4,4,4-tri group. A fluoro-3,3-difluorobutyl group, a 2-chloroethyl group, etc. are mentioned. Particularly preferred as R ⁸ and R ⁹ is a methyl group.

  In the formula (3), q is a positive number of 1 or more, but generally, when a high molecular weight silicone having a number of q of 100 or more is used, the obtained graft copolymer is often oily. . When a low molecular weight silicone having a q number of 100 or less is used, the resulting graft copolymer can be obtained in various forms such as oil, jelly, and solid depending on the type of monomer.

  Next, examples of the acrylic silane compound represented by the formula (4) include γ-methacryloxypropyldimethylchlorosilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropyldiphenylchlorosilane, γ-acryloxypropyldimethylchlorosilane, Examples include γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrichlorosilane, and the like. These acrylic silane compounds can be easily obtained by reacting a silicon compound and a compound having an aliphatic multiple bond in the presence of chloroplatinic acid according to the method described in JP-B-33-9969.

  For radical copolymerization in the production of the graft copolymer, a conventionally known method can be used, and a radiation irradiation method or a method using a radical polymerization initiator can be used. Furthermore, when copolymerizing by the ultraviolet irradiation method, a known sensitizer is used as a radical polymerization initiator, and when copolymerizing by electron beam irradiation, it is not necessary to use a radical polymerization initiator. The radical copolymer thus obtained is a comb-shaped graft copolymer having a repeating unit formed using a radical polymerizable monomer as a trunk and silicone as a branch. In addition, you may use together the monomer containing a hydroxyl group like 2-hydroxyethyl (meth) acrylate as a radically polymerizable monomer.

  Moreover, the graft copolymer in this invention can also utilize a commercial item, for example, Cymac US-150, US-270, US-350, US-450, Reseda GP-700 (above, Toagosei Co., Ltd.) Manufactured).

  The graft copolymer is preferably blended at a rate of 5 to 40 parts by mass with respect to 100 parts by mass of the matrix component. When the blending amount of the graft copolymer is 5 parts by mass or more, the alkali resistance is further improved. Further, when it is 40 parts by mass or less, coating unevenness is suppressed when the low refractive index layer is applied. A more preferable blending ratio is 10 to 30 parts by mass of the graft copolymer with respect to 100 parts by mass of the matrix component.

  Furthermore, various additives can be blended in the composition for forming a low refractive index layer in the present invention for the purpose of adjusting physical properties such as hardness, scratch resistance, and conductivity of the film.

  Examples of the organic solvent suitable for use in the coating material for forming the low refractive index layer include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, Aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, esters such as ethyl acetate, butyl acetate and γ-butyrolactone, ethers such as tetrahydrofuran and 1,4-dioxane And β-diketones such as acetylacetone and ethyl acetoacetate, and β-ketoesters.

  Examples of the method for coating the hard coat layer surface with the composition for forming a low refractive index layer in the present invention include a dipping method, a spin coat method, a flow coat method, a roll coat method, a spray coat method, a screen printing method, and the like. Although not particularly limited, since the film thickness can be easily controlled, it is preferable to perform the film thickness to a predetermined thickness by the dipping method, the spray coating method, and the roll coating method. After application, a cured film can be formed by heating or the like.

  The refractive index of the low refractive index layer is preferably 1.28 to 1.50, more preferably 1.30 to 1.45. The thickness of the low refractive index layer is preferably 40 to 300 nm, and more preferably 60 to 150 nm.

The antireflection film of the present invention preferably has a total light transmittance of 90% or more, and more preferably 92% or more. The total light transmittance can be measured according to JIS K 7361-1. When the total light transmittance is less than 90%, the transparency is slightly inferior, and when used as an antireflection film for a display, the image sharpness may be lowered.
The antireflection film of the present invention has a surface resistivity of 1.0 × 10 ¹² Ω / sq. Or less, preferably 1.0 × 10 ¹⁰ Ω / sq. More preferably, it is as follows.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these examples.

Example 1
A biaxially stretched polyethylene terephthalate film (refractive index: 1.65) having a thickness of 100 μm was coated with a water-dispersible polyester resin as an easy-adhesive layer at a thickness of 80 nm (refractive index: 1.58). PET (1) was applied, and a hard coat layer-forming coating material having the following composition was applied thereon so as to have a dry film thickness of 2.5 μm and dried. Subsequently, the coating was cured by irradiating ultraviolet rays with a high-pressure mercury lamp to form a hard coat layer (refractive index 1.64).
Next, a low refractive index layer-forming coating material A having the following composition was applied on the hard coat layer so as to have a dry film thickness of 70 nm (refractive index of 1.39 of the low refractive index layer), and dried. An antireflection film was produced.

(Hard coat layer forming paint)
・ Ionizing radiation curable resin 100 parts by mass Dipentaerythritol hexaacrylate (DPHA)
(Nippon Kayaku 6 functional acrylic UV curable resin, solid content 100%, refractive index 1.48)
-Gallium-doped zinc oxide (1) 1000 parts by mass
(200 mass parts solid content)
(Manufactured by Hakusui Tech, Pazette GK-40, solid content 20%, primary particle diameter 20 to 40 nm)
・ Zinc antimonate 333 parts by mass
(200 mass parts solid content)
(Nissan Chemical Co., Ltd., Celnax CX-Z610M-F2, solid content 60%, refractive index 1.7)
-Polymer having an unsaturated double bond copolymerizable at the terminal 20 parts by mass
(9 mass parts solid content)
(Macromonomer AA-6 manufactured by Toa Gosei Co., Ltd., terminal methacrylate polymethyl methacrylate, molecular weight 6000, solid content 45%, diluted with toluene)
・ 7 parts by weight of photopolymerization initiator (Irgacure (IR) 184, manufactured by Ciba Specialty Chemicals)
-Photopolymerization initiator 1 part by mass (Irgacure (IR) 907 manufactured by Ciba Specialty Chemicals)
UV absorber (1) Compound name: 8 parts by mass of benzotriazole UV absorber (trade name: TINUVIN 284-2, manufactured by Ciba Specialty Chemicals)
・ Solvent 120 parts by mass (methyl ethyl ketone (MEK) / propylene glycol monomethyl ether (PGM))

(Composition of paint A for forming low refractive index layer)
-The following matrix component A 3333 parts by mass (solid content 100 parts by mass)
-278 parts by mass of a hollow silica dispersion sol treated with the following silane coupling agent A
(Solid content 50 parts by weight)
・ Graft copolymer 67 parts by mass
(Solid content 20 parts by mass)
(Toagosei Co., Ltd., Cymac US-270, solid content 30%, comb-shaped graft polymer in which the trunk portion is an acrylic polymer and the branch portion is made of silicone)
・ Solvent 4850 parts by mass (Methyl isobutyl ketone (MIBK))

(Preparation of hollow silica dispersion sol treated with silane coupling agent A)
Hollow silica dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., ELCOM RK-1018SIV, solid content 20%, solvent is methyl isobutyl ketone (MIBK), average particle diameter of hollow silica is 40 nm) in 100 parts by mass, silane coupling agent A dispersion sol obtained by adding 10 parts by mass of A (TSL-8311, made by GE Toshiba Silicone, vinyltriethoxysilane, solid content 2%, solvent is methanol), stirring well, and silane coupling treatment. (Solid content 18%)

(Preparation of matrix component A)
A 1 liter flask equipped with a stirrer, a condenser and a thermometer was charged with 29.9 g (0.05 mol) of the following disilane compound (1) and 125 g of t-butanol and stirred at 25 ° C. .10 g of 1N aqueous acetic acid was added dropwise over 10 minutes. The mixture was further stirred at 25 ° C. for 20 hours to complete hydrolysis. To this, 2 g of aluminum acetylacetonate as a condensation catalyst and 1 g of polyether-modified silicone as a leveling agent were added, and the mixture was further stirred for 30 minutes. Paint prepared by diluting and adding 40 g of propylene glycol monomethyl ether and 40 g of diacetone alcohol. (Solid content 3%)
_{(CH 3 O) 3 Si-} C 2 H 4 -C 6 F 12 -C 2 H 4 -Si (OCH 3) 3 (1)

The following evaluation was performed about the obtained antireflection film.
(1) Minimum reflectance Using a spectrophotometer [manufactured by Shimadzu Corporation, Solid Spec 3700], the reflectance at a wavelength of 380 to 780 nm is measured, and the minimum value is recorded. If the waveform is wavy, smoothing processing is performed to obtain the minimum value.
(2) Total light transmittance It was measured using a turbidimeter [Nippon Denshoku Industries Co., Ltd. NDH2000] according to JIS K7136.
(3) Haze The haze was measured using a turbidimeter [Nippon Denshoku Industries Co., Ltd. NDH2000] according to JIS K 7136.
(4) Pencil hardness In accordance with JIS K 5400 8.4.2, a pencil [Mitsubishi Pencil Co., Ltd., Uni] is used to evaluate the scratch on the coating film.
(5) Steel wool resistance Steel wool [Nippon Steel Wool Co., Ltd., # 0000] is rolled and rubbed 10 times with a load of 200 g, and the state of the scratch is observed. judge.
○: No scratches at all.
Δ: 1 to 9 scratches are observed.
X: 10 or more scratches are observed.
(6) Surface resistivity It measured using the resistivity meter [Mitsubishi Chemical Corporation, Hirestar MCP-HT450].
(7) Curling property A sample is prepared in a size of 10 cm × 10 cm, and the curl heights at the four corners when the sample is placed on a horizontal surface are measured, and determined according to the following criteria.
○: curl height is less than 20 mm Δ: curl height is 20 mm or more and less than 50 mm x: curl height is 50 mm or more (8) Alkali resistance A 2% NaOH aqueous solution is dropped on the film surface and left for 20 minutes to wipe off and contaminate. The situation is visually judged according to the following criteria.
○: No contamination is seen.
Δ: Slightly contaminated
X: Significantly contaminated.
(9) Ultraviolet ray cutting property Using a spectrophotometer [manufactured by Shimadzu Corporation, Solid Spec 3700], the transmittance at 380 nm is measured and determined according to the following criteria.
○: Transmittance at 380 nm is less than 5% Δ: Transmittance at 380 nm is 5% or more and less than 50% X: Transmittance at 380 nm is 50% or more (10) Smog (whitening)
The obtained film is visually inspected under an incandescent lamp and judged according to the following criteria.
○: White cloud-like coating unevenness (whitening) is not recognized at all.
Δ: White cloud-like coating unevenness (whitening) is slightly observed.
X: White cloud-like coating unevenness (whitening) is large.
(11) Interference fringes Place an antireflection film on black paper and observe the interference fringes around the image of the fluorescent lamp by illuminating with a three-wavelength fluorescent lamp [Matsushita Electric Industrial Co., Ltd., Palook, 20W, daylight white]. The interference fringes are determined according to the following criteria.
A: No interference fringes are observed.
○: Interference fringes are hardly observed.
Δ: Interference fringes are faintly recognized.
X: Interference fringes are clearly recognized.

  The results are shown in Table 1 below.

Example 2
In Example 1, Example 1 was repeated except that 625 parts by mass of gallium-doped zinc oxide (1) (solid content of 125 parts by mass) and 208 parts by mass of zinc antimonate (solid content of 125 parts by mass) were used. . The results are shown in Table 1.

Example 3
In Example 1, the amount of DPHA used was changed to 50 parts by mass, and petalisitol triacrylate PETA (manufactured by Toagosei Co., Ltd., trifunctional acrylic ultraviolet curable resin, solid content 100%, refractive index 1.49). ) Was added, and 1375 parts by weight of gallium-doped zinc oxide (1) (solid content: 275 parts by weight) and 550 parts by weight of zinc antimonate (solid content: 275 parts by weight) were used. Example 1 was repeated. The results are shown in Table 1.

Example 4
In Example 1, Example 1 was repeated except that 1200 parts by mass of gallium-doped zinc oxide (1) (solid content of 240 parts by mass) and 267 parts by mass of zinc antimonate (solid content of 160 parts by mass) were used. . The results are shown in Table 1.

Example 5
In Example 1, Example 1 was repeated except that 800 parts by mass of gallium-doped zinc oxide (1) (solid content of 160 parts by mass) and 400 parts by mass of zinc antimonate (solid content of 240 parts by mass) were used. . The results are shown in Table 1.

Example 6
In Example 1, Example 1 was repeated except that 1600 parts by mass of gallium-doped zinc oxide (1) (solid content of 320 parts by mass) and 133 parts by mass of zinc antimonate (solid content of 80 parts by mass) were used. . The results are shown in Table 2.

Example 7
In Example 1, Example 1 was repeated except that 400 parts by mass of gallium-doped zinc oxide (1) (solid content of 80 parts by mass) and 533 parts by mass of zinc antimonate (solid content of 320 parts by mass) were used. . The results are shown in Table 2.

Example 8
In Example 1, Example 1 was repeated except that the thickness of the hard coat layer was changed to 4.0 μm. The results are shown in Table 2 below.

Example 9
In Example 1, 625 parts by mass (125 parts by mass of solids) of gallium-doped zinc oxide (1) and 208 parts by mass of zinc antimonate (125 parts by mass of solids) were used, and the thickness of the hard coat layer was 1. Example 1 was repeated except that it was changed to 5 μm. The results are shown in Table 2 below.

Example 10
In Example 1, except that the polymer having an unsaturated double bond copolymerizable at the terminal in the coating material for forming the hard coat layer (macromonomer AA-6 manufactured by Toa Gosei Co., Ltd.) was not used. 1 was repeated. The results are shown in Table 2 below.

Example 11
In Example 1, Example 1 was repeated except that the gallium-doped zinc oxide (1) was changed to the following gallium-doped zinc oxide (2). The results are shown in Table 3 below.
Gallium-doped zinc oxide (2): Hakusuitec Co., Ltd., passette GK-1, zinc oxide doped with gallium, solid content 20%, primary particle size 0.25 to 2 μm.

Example 12
In Example 1, Example 1 was repeated except that the ultraviolet absorbent (1) was changed to the following ultraviolet absorbent (2). The results are shown in Table 3 below.
Ultraviolet absorber (2): Compound name Benzophenone ultraviolet absorber (Ciba Japan, trade name CHIMASSORB 81)

Example 13
In Example 1, Example 1 was repeated except that the low refractive index layer-forming coating material A was changed to the following low refractive index layer-forming coating material B. The results are shown in Table 3 below.
Low refractive index layer-forming coating material B: A hollow silica dispersion sol treated with the silane coupling agent B in the composition of the low refractive index layer-forming coating material A was used.
Silane coupling agent B: KBM-5103, manufactured by Shin-Etsu Silicone Co., Ltd., 3-acryloxypropyltrimethoxysilane, solid content 2%, solvent is methanol

Example 14
In Example 1, Example 1 was repeated except that the low refractive index layer-forming coating material A was changed to the following low refractive index layer-forming coating material C. The results are shown in Table 3 below.
Low refractive index layer-forming coating material C: In the composition of the low refractive index layer-forming coating material A, the addition amount of the hollow silica dispersion sol treated with the silane coupling agent A is changed to 555 parts by mass (solid content 100 parts by mass). Other than that, it is the same prescription.

Example 15
In Example 1, Example 1 was repeated except that the low refractive index layer-forming coating material A was changed to the following low refractive index layer-forming coating material D. The results are shown in Table 3 below.
Low refractive index layer-forming coating material D: In the composition of the low refractive index layer-forming coating material A, the addition amount of the hollow silica dispersion sol treated with the silane coupling agent A is changed to 833 parts by mass (solid content 150 parts by mass). Other than that, it is the same prescription.

Comparative Example 1
In Example 1, Example 1 was repeated except that 375 parts by mass of gallium-doped zinc oxide (1) (75 parts by mass of solids) and 125 parts by mass of zinc antimonate (75 parts by mass of solids) were used. . The results are shown in Table 4.

Comparative Example 2
In Example 1, Example 1 was repeated except that 1750 parts by mass (solid content 350 parts by mass) of gallium-doped zinc oxide (1) and 583 parts by mass of zinc antimonate (solid content 350 parts by mass) were used. . The results are shown in Table 4.

Comparative Example 3
In Example 1, Example 1 was repeated except that 1900 parts by mass (solid content of 380 parts by mass) of gallium-doped zinc oxide (1) and 33 parts by mass of zinc antimonate (solid content of 20 parts by mass) were used. . The results are shown in Table 4.

Comparative Example 4
In Example 1, Example 1 was repeated except that 100 parts by mass of gallium-doped zinc oxide (1) (solid content of 20 parts by mass) and 633 parts by mass of zinc antimonate (solid content of 380 parts by mass) were used. . The results are shown in Table 4.

Comparative Example 5
In Example 1, Example 1 was repeated except that 2000 parts by mass (400 parts by mass of solid content) of gallium-doped zinc oxide (1) was used and no zinc antimonate was used. The results are shown in Table 4.

Comparative Example 6
In Example 1, Example 1 was repeated except that gallium-doped zinc oxide (1) was not used and 667 parts by mass of zinc antimonate (solid content of 400 parts by mass) was used. The results are shown in Table 5.

Comparative Example 7
In Example 1, Example 1 was repeated except that the thickness of the hard coat layer was changed to 0.2 μm. The results are shown in Table 5.

Comparative Example 8
In Example 1, Example 1 was repeated except that the thickness of the hard coat layer was changed to 6.0 μm. The results are shown in Table 5.

Comparative Example 9
In Example 1, Example 1 was repeated except that the low refractive index layer-forming coating material A was changed to the following low refractive index layer-forming coating material E. The results are shown in Table 6 below.
Low refractive index layer-forming coating material E: A formulation excluding the hollow silica dispersion sol treated with the silane coupling agent A in the composition of the low refractive index layer-forming coating material A.

Comparative Example 10
In Example 1, Example 1 was repeated except that the low refractive index layer-forming coating material A was changed to the following low refractive index layer-forming coating material F. The results are shown in Table 6 below.
Low refractive index layer forming coating F: In the composition of the low refractive index layer forming coating A, the hollow silica dispersion sol treated with the silane coupling agent A is changed to a hollow silica dispersion sol not treated with the silane coupling agent. The prescription which changed and added 250 mass parts (50 mass parts of solid content) of this.

Comparative Example 11
In Example 1, Example 1 was repeated except that the low refractive index layer-forming coating material A was changed to the following low refractive index layer-forming coating material G. The results are shown in Table 6 below.
Low refractive index layer-forming coating G: In the composition of the low refractive index layer-forming coating A, the hollow silica dispersion sol treated with the silane coupling agent A is changed to a hollow silica dispersion sol not treated with the silane coupling agent. The prescription which changed and added this 750 mass parts (solid content 150 mass parts).

The following items are derived from the above table.
In Example 1, a hard coat layer having a specific thickness and material configuration and a low refractive index layer having a specific material configuration were sequentially provided on a base film made of biaxially stretched polyethylene terephthalate. , Interference fringes are inconspicuous, minimum reflectance is low, transparency, steel wool resistance, antistatic properties, curling properties are excellent, and the balance between transparency and antistatic properties is excellent, improving alkali resistance In addition, it was possible to provide an antireflection film that is excellent in ultraviolet cut-off property and does not generate smog (whitening) during production.
Example 2 was an example in which 125 parts by mass of gallium-doped zinc oxide and 125 parts by mass of zinc antimonate were added, and the interference fringes were evaluated as o. The minimum reflectance also deteriorated slightly. The other performance was good.
Example 3 was an example in which 275 parts by mass of gallium-doped zinc oxide and 275 parts by mass of zinc antimonate were added, and showed the same performance as Example 1.
Example 4 was an example in which 240 parts by mass of gallium-doped zinc oxide and 160 parts by mass of zinc antimonate were added, and showed the same performance as Example 1.
Example 5 was an example in which 160 parts by mass of gallium-doped zinc oxide and 240 parts by mass of zinc antimonate were added, and showed the same performance as Example 1.
Example 6 was an example in which 320 parts by mass of gallium-doped zinc oxide and 80 parts by mass of zinc antimonate were added, and the surface resistivity was slightly deteriorated. The other performance was good.
In Example 7, 80 parts by mass of gallium-doped zinc oxide and 320 parts by mass of zinc antimonate were added, and the haze was slightly deteriorated. The other performance was good.
In Example 8, the thickness of the hard coat layer was set to 4.0 μm, and the interference fringes were evaluated as “Good”. The other performance was good.
Example 9 was an example in which 125 parts by mass of gallium-doped zinc oxide and 125 parts by mass of zinc antimonate were added and the thickness of the hard coat layer was 1.5 μm, and the minimum reflectance was slightly deteriorated. The other performance was good.
-Example 10 is an example which did not add a macromonomer, and curl property deteriorated a little. The other performance was good.
-Example 11 is an example which uses gallium dope zinc oxide (2), and haze deteriorated a little. The other performance was good.
-Example 12 is an example which uses a ultraviolet absorber (2), and the ultraviolet cut property deteriorated a little. The other performance was good.
-Example 13 is the example which uses the coating material B for low refractive index layer formation, and smog (whitening) deteriorated a little. The other performance was good.
-Example 14 is the example which uses the coating material C for low refractive index layer formation, and although the minimum reflectance became a favorable value, alkali resistance deteriorated a little. The other performance was good.
-Example 15 is an example using the coating material D for low refractive index layer formation, and although the minimum reflectance became a favorable value, alkali resistance deteriorated a little. The other performance was good.

Comparative Example 1 was an example in which 75 parts by mass of gallium-doped zinc oxide and 75 parts by mass of zinc antimonate were added, and was outside the scope of the present invention. In addition, the minimum reflectance was slightly deteriorated.
Comparative Example 2 was an example in which 350 parts by mass of gallium-doped zinc oxide and 350 parts by mass of zinc antimonate were added, and was outside the scope of the present invention. In addition, the steel wool resistance was slightly deteriorated.
Comparative Example 3 was an example in which 380 parts by mass of gallium-doped zinc oxide and 20 parts by mass of zinc antimonate were added, and the surface resistivity was deteriorated because it was outside the scope of the present invention.
Comparative Example 4 was an example in which 20 parts by mass of gallium-doped zinc oxide and 380 parts by mass of zinc antimonate were added, and the haze was deteriorated because it was outside the scope of the present invention.
Comparative Example 5 was an example in which 400 parts by mass of gallium-doped zinc oxide was added and zinc antimonate was not added, and was outside the scope of the present invention, so the surface resistivity was deteriorated.
Comparative Example 6 was an example in which 400 parts by mass of zinc antimonate was added and gallium-doped zinc oxide was not added, and the haze was deteriorated because it was outside the scope of the present invention.
Comparative Example 7 is an example in which the thickness of the hard coat layer was 0.2 μm, and was outside the scope of the present invention, so that interference fringes and steel wool resistance were evaluated as x.
Comparative Example 8 is an example in which the thickness of the hard coat layer is 6.0 μm and is outside the scope of the present invention.
Comparative Example 9 is an example in which the coating material E for forming a low refractive index layer was used, and was outside the scope of the present invention, so the minimum reflectance deteriorated.
Comparative Example 10 is an example in which the coating material F for forming a low refractive index layer was used, and was outside the scope of the present invention, so smog (whitening) was evaluated as x.
Comparative Example 11 is an example in which the coating material G for forming a low refractive index layer was used, and was outside the scope of the present invention. Therefore, smog (whitening) and alkali resistance were evaluated as x.

  The antireflection film of the present invention has interference fringes inconspicuous, low minimum reflectance, excellent properties such as transparency, steel wool resistance, antistatic properties and curling properties, and a balance between transparency and antistatic properties. Excellent anti-alkali and UV-blocking properties, and does not generate smog (whitening) during production, making it useful for anti-reflection of the surface of liquid crystal display devices, plasma display panels, personal computers, TVs, touch panels, etc. is there.

Claims (9)

An antireflection film having a hard coat layer on a base film made of biaxially stretched polyethylene terephthalate, and further having a low refractive index layer on the hard coat layer,
The hard coat layer has a thickness of 0.5 to 5 μm,
The hard coat layer is a mixture of gallium-doped zinc oxide and zinc antimonate on 100 parts by mass of ionizing radiation curable resin containing polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule ( However, it is formed by blending 200 to 600 parts by mass of gallium-doped zinc oxide: zinc antimonate = 9: 1 to 1: 9 (mass ratio) and curing this,
The low refractive index layer is a hollow treated with a disilane compound having a divalent organic group containing one or more fluorine atoms or a matrix component mainly composed of a (partial) hydrolyzate thereof, and a silane coupling agent. Formed from a composition for forming a low refractive index layer containing silica particles,
The antireflective film, wherein the composition for forming a low refractive index layer is formed by blending 20 to 160 parts by mass of hollow silica particles treated with the silane coupling agent with respect to 100 parts by mass of the matrix component. .   The antireflection film according to claim 1, wherein 5 to 20 parts by mass of a polymer having an unsaturated double bond copolymerizable at a terminal is further blended with 100 parts by mass of the ionizing radiation curable resin.   The antireflection film according to claim 1, further comprising 0.5 to 20 parts by mass of an ultraviolet absorber in 100 parts by mass of the ionizing radiation curable resin.   The antireflection film according to claim 3, wherein the ultraviolet absorber is benzotriazole-based.   The antireflection film according to claim 1, wherein the polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule is dipentaerythritol hexaacrylate.   The primary particle diameter of the said gallium dope zinc oxide is 5-100 nm, The antireflection film of Claim 1 characterized by the above-mentioned. The disilane compound is represented by the following formula (1):
^{_{X m R 1 3-m Si}} -Y-SiR 1 3-m X m (1)
Wherein R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a divalent organic group containing one or more fluorine atoms, X is a hydrolyzable group, m is 1, 2 or 3. is there.)
The antireflection film according to claim 1, wherein   The average particle diameter of the hollow silica particle processed with the said silane coupling agent is 5-100 nm, The antireflection film of Claim 1 characterized by the above-mentioned.   The antireflection film according to claim 1, wherein the silane coupling agent is a vinylsilane coupling agent.